EP4022099A1 - Environmentally friendly process for tanning hides - Google Patents
Environmentally friendly process for tanning hidesInfo
- Publication number
- EP4022099A1 EP4022099A1 EP21754838.7A EP21754838A EP4022099A1 EP 4022099 A1 EP4022099 A1 EP 4022099A1 EP 21754838 A EP21754838 A EP 21754838A EP 4022099 A1 EP4022099 A1 EP 4022099A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- weight
- hide
- respect
- amount
- water
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000000034 method Methods 0.000 title claims abstract description 73
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 72
- 239000000203 mixture Substances 0.000 claims description 47
- 238000011282 treatment Methods 0.000 claims description 28
- 150000001991 dicarboxylic acids Chemical class 0.000 claims description 21
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 20
- 239000001166 ammonium sulphate Substances 0.000 claims description 20
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 20
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 19
- 238000007792 addition Methods 0.000 claims description 16
- 238000002803 maceration Methods 0.000 claims description 14
- 238000002360 preparation method Methods 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 13
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 12
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 11
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 10
- 238000002791 soaking Methods 0.000 claims description 10
- 230000000844 anti-bacterial effect Effects 0.000 claims description 9
- 239000013527 degreasing agent Substances 0.000 claims description 9
- 239000000839 emulsion Substances 0.000 claims description 9
- 150000003839 salts Chemical class 0.000 claims description 9
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 claims description 9
- 239000001648 tannin Substances 0.000 claims description 9
- 229920001864 tannin Polymers 0.000 claims description 9
- 235000018553 tannin Nutrition 0.000 claims description 9
- -1 2-propylethyl alcohol Chemical compound 0.000 claims description 8
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical group [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 8
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 8
- 235000019253 formic acid Nutrition 0.000 claims description 7
- 159000000000 sodium salts Chemical class 0.000 claims description 7
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 7
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 6
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 235000019270 ammonium chloride Nutrition 0.000 claims description 6
- 239000011651 chromium Substances 0.000 claims description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 6
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 claims description 6
- 102000004190 Enzymes Human genes 0.000 claims description 5
- 108090000790 Enzymes Proteins 0.000 claims description 5
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 5
- 239000004280 Sodium formate Substances 0.000 claims description 5
- 235000011037 adipic acid Nutrition 0.000 claims description 5
- 229910052804 chromium Inorganic materials 0.000 claims description 5
- 230000002045 lasting effect Effects 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 150000004714 phosphonium salts Chemical class 0.000 claims description 5
- 239000001632 sodium acetate Substances 0.000 claims description 5
- 235000017281 sodium acetate Nutrition 0.000 claims description 5
- 235000019254 sodium formate Nutrition 0.000 claims description 5
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 claims description 4
- CFKMVGJGLGKFKI-UHFFFAOYSA-N 4-chloro-m-cresol Chemical compound CC1=CC(O)=CC=C1Cl CFKMVGJGLGKFKI-UHFFFAOYSA-N 0.000 claims description 4
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 4
- 239000001361 adipic acid Substances 0.000 claims description 4
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 claims description 4
- LLEMOWNGBBNAJR-UHFFFAOYSA-N biphenyl-2-ol Chemical compound OC1=CC=CC=C1C1=CC=CC=C1 LLEMOWNGBBNAJR-UHFFFAOYSA-N 0.000 claims description 4
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 4
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 4
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 4
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 4
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 claims description 4
- HYHCSLBZRBJJCH-UHFFFAOYSA-M sodium hydrosulfide Chemical compound [Na+].[SH-] HYHCSLBZRBJJCH-UHFFFAOYSA-M 0.000 claims description 4
- 239000004094 surface-active agent Substances 0.000 claims description 4
- 239000000920 calcium hydroxide Substances 0.000 claims description 3
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 3
- 235000011116 calcium hydroxide Nutrition 0.000 claims description 3
- VTIIJXUACCWYHX-UHFFFAOYSA-L disodium;carboxylatooxy carbonate Chemical compound [Na+].[Na+].[O-]C(=O)OOC([O-])=O VTIIJXUACCWYHX-UHFFFAOYSA-L 0.000 claims description 3
- 229940045872 sodium percarbonate Drugs 0.000 claims description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 3
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 3
- 235000011152 sodium sulphate Nutrition 0.000 claims description 3
- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid Chemical compound NS(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 claims description 3
- 229940061334 2-phenylphenol Drugs 0.000 claims description 2
- DMSMPAJRVJJAGA-UHFFFAOYSA-N benzo[d]isothiazol-3-one Chemical compound C1=CC=C2C(=O)NSC2=C1 DMSMPAJRVJJAGA-UHFFFAOYSA-N 0.000 claims description 2
- 230000000295 complement effect Effects 0.000 claims description 2
- 239000003599 detergent Substances 0.000 claims description 2
- 235000010292 orthophenyl phenol Nutrition 0.000 claims description 2
- 239000003242 anti bacterial agent Substances 0.000 claims 2
- 238000005554 pickling Methods 0.000 abstract description 15
- 241001465754 Metazoa Species 0.000 abstract description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 24
- 239000003795 chemical substances by application Substances 0.000 description 15
- 230000001046 anti-mould Effects 0.000 description 13
- 239000002546 antimould Substances 0.000 description 13
- 239000011780 sodium chloride Substances 0.000 description 12
- 239000012855 volatile organic compound Substances 0.000 description 11
- 239000003921 oil Substances 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- 239000010985 leather Substances 0.000 description 8
- 238000005259 measurement Methods 0.000 description 7
- 238000004321 preservation Methods 0.000 description 6
- 150000007942 carboxylates Chemical group 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000005238 degreasing Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 230000008961 swelling Effects 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- 241000283690 Bos taurus Species 0.000 description 2
- 102000008186 Collagen Human genes 0.000 description 2
- 108010035532 Collagen Proteins 0.000 description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- 241001494479 Pecora Species 0.000 description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 2
- 239000000292 calcium oxide Substances 0.000 description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- 244000309466 calf Species 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- GRWVQDDAKZFPFI-UHFFFAOYSA-H chromium(III) sulfate Chemical compound [Cr+3].[Cr+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GRWVQDDAKZFPFI-UHFFFAOYSA-H 0.000 description 2
- 239000011696 chromium(III) sulphate Substances 0.000 description 2
- 235000015217 chromium(III) sulphate Nutrition 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000008030 elimination Effects 0.000 description 2
- 238000003379 elimination reaction Methods 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 239000003925 fat Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- 230000003204 osmotic effect Effects 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 238000009938 salting Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 230000037303 wrinkles Effects 0.000 description 2
- SDGNNLQZAPXALR-UHFFFAOYSA-N 3-sulfophthalic acid Chemical compound OC(=O)C1=CC=CC(S(O)(=O)=O)=C1C(O)=O SDGNNLQZAPXALR-UHFFFAOYSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- 241000283707 Capra Species 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 1
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001279 adipic acids Chemical class 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- JXLHNMVSKXFWAO-UHFFFAOYSA-N azane;7-fluoro-2,1,3-benzoxadiazole-4-sulfonic acid Chemical compound N.OS(=O)(=O)C1=CC=C(F)C2=NON=C12 JXLHNMVSKXFWAO-UHFFFAOYSA-N 0.000 description 1
- 238000009529 body temperature measurement Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 150000001844 chromium Chemical class 0.000 description 1
- VQWFNAGFNGABOH-UHFFFAOYSA-K chromium(iii) hydroxide Chemical class [OH-].[OH-].[OH-].[Cr+3] VQWFNAGFNGABOH-UHFFFAOYSA-K 0.000 description 1
- 229920001436 collagen Polymers 0.000 description 1
- 239000006071 cream Substances 0.000 description 1
- 230000035617 depilation Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000002255 enzymatic effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 150000004674 formic acids Chemical class 0.000 description 1
- 238000010353 genetic engineering Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 102000034238 globular proteins Human genes 0.000 description 1
- 108091005896 globular proteins Proteins 0.000 description 1
- 150000002311 glutaric acids Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000001151 other effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 206010033675 panniculitis Diseases 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000035755 proliferation Effects 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000003307 slaughter Methods 0.000 description 1
- 239000004289 sodium hydrogen sulphite Substances 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 230000003019 stabilising effect Effects 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 210000004304 subcutaneous tissue Anatomy 0.000 description 1
- 150000003444 succinic acids Chemical class 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- YIEDHPBKGZGLIK-UHFFFAOYSA-L tetrakis(hydroxymethyl)phosphanium;sulfate Chemical compound [O-]S([O-])(=O)=O.OC[P+](CO)(CO)CO.OC[P+](CO)(CO)CO YIEDHPBKGZGLIK-UHFFFAOYSA-L 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C14—SKINS; HIDES; PELTS; LEATHER
- C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
- C14C3/00—Tanning; Compositions for tanning
- C14C3/02—Chemical tanning
- C14C3/28—Multi-step processes
-
- C—CHEMISTRY; METALLURGY
- C14—SKINS; HIDES; PELTS; LEATHER
- C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
- C14C1/00—Chemical treatment prior to tanning
- C14C1/04—Soaking
-
- C—CHEMISTRY; METALLURGY
- C14—SKINS; HIDES; PELTS; LEATHER
- C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
- C14C1/00—Chemical treatment prior to tanning
- C14C1/06—Facilitating unhairing, e.g. by painting, by liming
- C14C1/065—Enzymatic unhairing
-
- C—CHEMISTRY; METALLURGY
- C14—SKINS; HIDES; PELTS; LEATHER
- C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
- C14C1/00—Chemical treatment prior to tanning
- C14C1/08—Deliming; Bating; Pickling; Degreasing
-
- C—CHEMISTRY; METALLURGY
- C14—SKINS; HIDES; PELTS; LEATHER
- C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
- C14C3/00—Tanning; Compositions for tanning
- C14C3/02—Chemical tanning
- C14C3/04—Mineral tanning
- C14C3/06—Mineral tanning using chromium compounds
-
- C—CHEMISTRY; METALLURGY
- C14—SKINS; HIDES; PELTS; LEATHER
- C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
- C14C3/00—Tanning; Compositions for tanning
- C14C3/02—Chemical tanning
- C14C3/08—Chemical tanning by organic agents
- C14C3/10—Vegetable tanning
Definitions
- the present invention refers to an innovative process for the tanning of animal hides characterised, compared to currently adopted processes, by the non-adoption of the step known in the industry as “pickling”, which is one of the main sources of pollution caused by the tanning industry.
- the invention also concerns hides tanned by the new process.
- STATE OF THE ART Tanning is the treatment to which the hides are subjected in order to transform them into leather, thus allowing their preservation indefinitely and the processing to make them suitable for use in various industrial sectors, including furniture and clothing, leather goods industry (bags, shoes and leather accessories) and in the automotive sector.
- Hide preservation treatments from the slaughter of the animals to tanning (and possible further subsequent treatments), have been known for centuries and have many variations; it is not possible to give an exhaustive description of these treatments here, for which reference should be made to specialised manuals, such as the book Tanning Chemistry: The Science of Leather, Anthony D. Covington and William R. Wise, Royal Society of Chemistry, 2 nd Edition, 2019.
- this operation must be carried out as quickly as possible after killing the animal, and consists in creating conditions inside the hide that prevent the development of microorganisms that would cause the putrefaction thereof.
- the most widely used methods for this purpose are salting and drying;
- this is one of the fundamental operations of the tanning process, and allows various effects to be obtained.
- This operation is carried out by treating the hides with calcium hydroxide (Ca(OH)2), which brings the pH of the bath to values around 12.5, in the presence of reducing agents, particularly sodium sulphide (Na2S).
- reducing agents particularly sodium sulphide (Na2S).
- Na2S sodium sulphide
- the main effects of liming are the depilation of the hide and its swelling and turgidity due to osmotic pressure caused by the high concentration of Na + , Ca 2+ and OH ions.
- Deliming the calcined hide is swollen and strongly alkaline, and in this state could not be subjected to the subsequent chemical operations. Deliming serves to lower the pH of the hide to around 8-9, eliminate swelling and turgidity, and eliminate calcium hydroxide and sodium sulphide. This operation is carried out with mildly acidic chemicals.
- Ammonium sulphate is generally used for cowhides, but other products such as weak organic acids (lactic acid, glycolic acid, etc.), sulphophthalic acid, sodium bisulphite and the like, or mixtures of these compounds, may also be used;
- - Maceration Maceration is an enzymatic operation whose purpose is to complete deliming, eliminate residues of other unhelpful interfibrillar substances, loosen the fibrous structure of the hide so as to facilitate the expulsion of the pigments (melanins) and hair roots remained still embedded in the hide and produce a softer leather.
- Baths of animal pancreatic enzymes possibly obtained from bacteria modified by genetic engineering, can be used for the operation. This operation can be carried out mildly, or not at all, if the intention is to produce a stiff and little flexible leather;
- the pH of the hide is brought to a value between about 3 and 4, generally using a mixture of sulphuric and formic acids, to prepare it for tanning.
- the aim is both to prevent the formation of chromium hydroxides (which occurs at pH values above 4-4.5), which would make the addition of the element useless, and to neutralize the free carboxylate groups produced in the liming step by forming R-COOH carboxyl groups.
- carboxylate groups are extremely reactive towards tanning metals, particularly Cr 3+ ions, so that the reaction would occur very quickly and effectively with the carboxylate groups on the surface of the hide, preventing further penetration of the tanning agent into the hide.
- the hide deriving from the pickling process is subjected to the actual tanning process, the chemical operation that transforms the still putrescible hide into an imputrescible material, i.e. leather.
- tanning There are many types of tanning, but the most common ones are chrome tanning (about 80-90% of all the leathers produced worldwide are chrome tanned) and tanning with mixtures of synthetic and vegetable tannins, aldehydes, particularly glutaraldehyde, and metallic salts, particularly of aluminium and zirconium.
- the product obtained by chrome tanning has a light blue-green colour and is referred to in the industry as “wet blue”, while tanning by mixtures of tannins, aldehydes and metallic salts (of metals other than chrome) gives an essentially white product and the product obtained is referred to as “wet white”.
- a tanning process may comprise other steps, such as fleshing (mechanical removal of residues of subcutaneous tissues), carried out before or, preferably, immediately after liming; splitting in the case of very thick hides (typically cowhides, while thinner sheep hides do not require or do not allow this operation), also carried out after liming and which consists in forcing the hide, by passing between two rollers, against a blade which divides it into two layers in a parallel manner to its surface; and degreasing, an operation carried out (normally using surfactants) between maceration and tanning when necessary, i.e. in the case of hides still containing high amounts of fat after maceration which could interfere with the tanning.
- fleshing mechanical removal of residues of subcutaneous tissues
- splitting in the case of very thick hides (typically cowhides, while thinner sheep hides do not require or do not allow this operation)
- degreasing an operation carried out (normally using surfactants) between maceration and tanning when necessary, i.e. in the
- pickling is a fundamental and necessary step in known tanning processes, but it is also one of the steps that causes the greatest environmental problems; after this step, a solution containing sulphates and, above all, high amounts of sodium chloride are discharged.
- Purification plants are able to reduce practically all the pollutants present in the waste water of the tanning processes, except for sodium chloride which therefore remains in the waste water.
- Sodium chloride is not a toxic or harmful product, but it strongly alters the environment of rivers and lakes into which the discharges of the tanning plants flow, with strong impacts on the flora and fauna of these environments.
- Patent application US 2005/0268671 A1 describes a process for the tanning of hides which has the stated purpose of achieving a better fixation of chromium salts in the wet blue tanning, and thus a lower dispersion of these salts in the environment. According to the document, this would be possible with a step of preparation for tanning carried out at higher pH values than those traditionally adopted, and which further makes it possible to reduce or even avoid the use of sodium chloride in the pickling step.
- sodium chloride is always used in relevant amounts, between 5 and 7% with respect to the weight of the hide, which are characteristic of the pickling steps of the prior art; moreover, no indicative data is reported on the quality, type (e.g. of cow, sheep, goat, etc.) and weight check (e.g. of cow 36 kg+ or above 40 kg, etc.) of the hides obtained according to the described tanning process.
- the present invention in a first aspect thereof relates to a process for the tanning of hides which includes the steps of soaking, liming, deliming, maceration, preparation for tanning, and tanning, characterized in that in the step of preparation for tanning the hides are treated with a liquid mixture consisting of:
- - a salt selected from sodium acetate and sodium formate or mixtures thereof in an amount between 1 and 2% by weight with respect to the weight of the hide.
- the invention concerns a hide tanned by the process described above.
- Fig. 1 shows schematically the experimental set-up for measuring the quality of a tanned hide (measurement of shrinkage temperature).
- the process of the invention comprises a series of steps carried out according to traditional methods, with the pickling being replaced by the characterising step mentioned above.
- a typical process of the invention includes steps of soaking, liming, deliming, maceration, preparation for tanning, and tanning carried out as described below.
- Soaking is carried out with a first step of continuous washing with running water for one hour or discontinuously, for example with the addition of two successive aliquots of water each in an amount of about twice the weight of the hide; and a second step of treatment in a drum with an amount of water of about twice the weight of the hide, for 16-24 hours.
- salts can be added to the water to give the solution a basic pH, e.g. sodium bicarbonate, or surfactant detergents.
- the temperature of the soaking step is preferably around 20-25 °C, and in any case not higher than 45 °C; in case of temperatures higher than 25 °C, an antibacterial product (anti-mould agent) must be added to the water to prevent the proliferation of micro-organisms that could alter the hide.
- the liming step can be carried out in any way known in the industry. This step is preferably carried out at room temperature, with a weight of water about double that of the hide to be treated, Ca(OH)2 in an amount between 3 and 5%, and sodium sulphide (Na2S) normally between 2 and 3% or sodium hydrosulphide (NaHS) in an amount between 0.5 and 1%. This step is protracted for a time between 18 and 36 hours, commonly between 21 and 24 hours.
- the deliming step is carried out at a temperature of about 30 to 38 °C, preferably in two successive phases, each carried out with an amount of water equal to the weight of hide to be treated, by draining the water between one phase and the next, and in which the second phase is carried out at a slightly higher temperature (e.g., 2 °C) than the first.
- the total time of the deliming step is about 3 to 4 hours.
- this step are used altogether, subdivided into the two phases: - a mixture containing between 40 and 45% of ammonium chloride (NhUCI), between 20 and 30% of one or more C4-C6 dicarboxylic acids, and between 0.5 and 1.5% of sulfamic acid (H2NSO3H), with the balance to 100% consisting of ammonium sulphate ((NhU ⁇ SC ); this mixture is added in this step in amounts between about 0.8 and 1.5% in the case of split hides and between 1.5 and 3% in the case of unsplit hides;
- NhUCI ammonium chloride
- H2NSO3H sulfamic acid
- a degreaser between 0.3 and 1.5% of a degreaser known in the field.
- a degreaser one can mention a liquid mixture consisting of about 54-58% by weight of 2-propylethyl alcohol ethoxylate (a commercially available component with CAS registry no. 160875-66-1), between 2 and 3% of sodium salts of sulphates of C12- C14 alcohol ethoxylates (CAS no. 68891 -38-3) and between 0.01 and 0.04% of 1 ,2- benzisothiazol-3(2/-/)-one (CAS no. 2634-33-5); also in this mixture the balance to 100% consists of ammonium sulphate.
- the maceration step is carried out at a temperature between 30 and 37 °C, with amounts of water between about 0.5 and 1.5 times the weight of the hide to be treated, for a total time between 3 and 5 hours.
- This step is completed by a series of washes, carried out with an amount of water between 2 and 4 times the weight of the hide.
- Pancreatic enzymes are added to the water of the maceration step in amounts between 0.1 and 2%.
- other components may be added to the water, for example up to about 0.5% by weight of a degreaser (e.g.
- the characterizing step of the process of the invention is the preparation for tanning one, which is carried out without using sodium chloride.
- This step is carried out at a temperature between 15 and 25 °C, preferably at 20 °C, for a time between 1 and 2.5 hours, with an amount of water between 40 and 60% with respect to the weight of the hides to be treated.
- water is added with:
- An antibacterial product can be added to the treatment water in amounts between 0.1 and 0.2%.
- Antibacterial (or anti-mould) products for tanning processes are widely available commercially; a possible product of this type comprises 25-35% by weight of sodium salt of 4-chloro-3-methylphenol, 8-12% of 2-phenylphenol, 11 - 15% of diethylene glycol and 12-14% of sodium hydroxide, with water as a 100% complement.
- the step before tanning of the invention offers other environmental advantages.
- the sulphonate-based oil described above has a very low content of volatile organic compounds (often also indicated with the corresponding abbreviation VOC).
- VOC volatile organic compounds
- a low VOC value of the tanned hides allows having a very low environmental impact, both in domestic use and in the workplace, and even more so in small spaces such as aircraft, ship hulls and especially car interiors.
- VDA 277:1995-01 based on the measurement of the equilibrium composition of the atmosphere in an enclosed space above the sample after static heating to 120 °C for 5 hours
- VDA 278:2011 based on the thermal desorption method
- the method VDA 278:2011 also allows determining the release of condensable volatile compounds (referred to in the sector as FOG).
- the tanned hide is typically subjected to further treatments such as retanning, after which it is pressed, split, shaved up to the thickness of 1.1 -1.2 mm and finally subjected to analytical checks of the release of volatile compounds; tests of this type carried out on the hides tanned by the process of the invention have resulted in VOC values equal to or less than 0.01 % by weight of the sulphonated oil used.
- the process of the invention comprises the actual tanning step.
- This step is carried out by adding the compounds listed below directly to the bath derived from the previous step, which is not unloaded from the drum.
- Tanning generally lasts between 16 and 20 hours and requires the use of various compounds added to the bath at different times.
- the compounds used and the timings of their additions vary depending on whether the tanning is for wet blue productions or the tanning is for wet white productions.
- a Cr 3+ salt e.g. basic chromium (III) sulphate (Cr(OFI)S04), possibly in a mixture with sodium sulphate, in an amount between 5 and 8%, between 0.5 and 0.8% of the above-described mixture of succinic, glutaric and adipic acids and about 0.2% of an anti-mould agent are added to the bath, leaving the system under rotation in the drum for 8 hours.
- Formic acid is then added in amounts between 0.3 and 0.5% allowing to react for 2 hours.
- An anti-mould agent (0.1 %) and an alkaline compound (0.4%), which has the function of stabilising and fixing the chromium on the protein fibres of the hide, are then added, allowing to react for 4 hours; commonly the alkaline compound is calcium oxide or a mixture containing it.
- the alkaline compound is calcium oxide or a mixture containing it.
- one or more washes are carried out with cold water (20 °C) in a total amount of about one and a half times the weight of the hide, with possible additions of small amounts (0.1 % each) of formic acid and anti-mould agent, for a total time of about 2 hours and a half.
- the drum is unloaded and the hides are recovered and sent to the steps following the tanning.
- a tanning agent generally a phosphonium salt or a mixture of phosphonium salts (e.g. tetrakis(hydroxymethyl)phosphonium sulphate, (P(CFl20FI)4)2S04) in an amount between 2 and 4% and an anti-mould agent in an amount between 0.3 and 0.5% are initially added, and the drum is rotated for at least three hours; the tanning agent is generally used in the form of a 50% by weight aqueous solution. The hides are then allowed to rest in the bath without rotation for about 8 hours (conveniently, this step is carried out overnight).
- a tanning agent generally a phosphonium salt or a mixture of phosphonium salts (e.g. tetrakis(hydroxymethyl)phosphonium sulphate, (P(CFl20FI)4)2S04) in an amount between 2 and 4% and an anti-mould agent in an amount between 0.3 and 0.5% are initially added, and the drum is rotated for at least three
- sodium bicarbonate NaFICCb
- sodium bicarbonate NaFICCb
- sodium percarbonate sodium bicarbonate
- the drum is unloaded and are added water at 40 °C in an amount by weight about the same as that of the hide, tannins (natural or synthetic) in an amount of about 4-5%, between 0.1 and 0.8% of an emulsion containing between 45 and 60% by weight of water and between 40 and 55% by weight of an oil consisting of one or more sulphonates of general formula R-SCbFI, wherein R is a C4-C20 alkyl radical (preferably C6-C14, more preferably C12-C14), and an amount between 0.1 and 0.2% of an anti-mould agent.
- R-SCbFI general formula R-SCbFI
- the system is allowed to react in the drum under stirring for about three hours, after which the drum is unloaded and the hides are washed with an amount of cold water equal to about twice the weight of the hides for about 10 minutes, finally unloading the drum and recovering the hides which are sent to the steps following the tanning.
- the invention concerns a hide tanned by the process described above.
- the tanned hide of the invention exhibits chemical stability (resistance to rot) and physical-mechanical characteristics comparable to, or even better than, the hides obtained by conventional tanning processes. Furthermore, the hides obtained by this process consistently showed a shrinkage temperature, Tg, above 75 °C in the case of tanning with tannins, and above 100 °C in the case of chromium tanning.
- the samples of hide tanned by the process of the invention are tested in the examples by measuring the shrinkage temperature according to ISO 3380.
- the method consists of slowly heating a specimen in water and measuring the temperature at which a sudden shrinkage of the sample occurs.
- the instrument for carrying out the test is shown schematically in Fig. 1 .
- the sample, 10, is completely immersed into water, initially at a temperature of 20 ⁇ 2 °C, inside a container 11 ; the lower end of the sample is blocked with a fixed clamp 12, while the upper end is hooked to a mobile clamp 13 connected to a movement indicator 14 (an index pivoted at one end at the centre of a quadrant 15); a sample pretensioner 16, which exerts on the sample a force equivalent to a weight of 3 g, is also connected to the same axis on which the index is pivoted.
- thermometer 17 Immersed in the water, near the centre of the sample, there is a thermometer 17 (in the set-up used in the tests, the thermometer was an IKA ® ETS-D5 electronic digital thermometer, from the company IKA ® -Werke GmbFI & Co. KG, Staufen, Germany).
- the temperature of the water is raised slowly (2 °C/min) by means of an electric heater in a glass or quartz sheath, immersed in the water in the lower part of the container (not shown in the figure).
- Tg shrinkage temperature
- the sample undergoes a sudden and irreversible shrinkage, which is visualised by the shift of the indicator 14.
- the measurement has an accuracy of ⁇ 0.5 °C.
- This example refers to the preparation of a wet blue tanning process (with chromium) according to the invention.
- the deliming step was carried out in three successive steps.
- non-ionic degreaser consisting of 2-propylethyl alcohol ethoxylate (content in the mixture 58%), 3% sodium salts of sulphates of C12-C14 alcohol ethoxylates and 0.04% 1 ,2-benzylisothiazol-3(2/-/)-one, the balance to 100% consisting of ammonium sulphate.
- the second phase of the deliming step was carried out under the same conditions and in the same way as the first step, the only difference being that the water temperature was 34 °C.
- the same components as in the first two steps were used, but in different amounts: 50% water at 36 °C, 3% of the mixture containing the C4-C6 dicarboxylic acids, 0.5% ammonium sulphate and 0.25% of the above-mentioned degreasing mixture were used; treatment in this third step was continued for two hours, at the end of which the drum was not unloaded from the solution.
- Maceration was then carried out.
- 0.2% of the mixture containing dicarboxylic acids described above and 0.2% of ammonium sulphate were added to the bath of the last delim ing step (at 36 °C) and the hides were treated with this solution for 30 minutes; then 1% of a commercial pancreatic enzyme was added and the treatment was continued for 90 minutes; finally the bath was unloaded from the drum.
- two washes were carried out, the first one lasting 20 minutes with 100% water at 20 °C and 0.3% of the above- mentioned degreasing mixture, followed by drum unloading; the second wash was carried out with sole water (100%) at 20 °C for 10 minutes followed by drum unloading.
- the step of the preparation for tanning, characteristic of the invention was then carried out.
- 1 % sodium acetate and 0.5% of a mixture of powdered C4-C6 dicarboxylic acids were then added and the treatment continued for two hours.
- the system was then allowed to rest overnight, with the drum rotating for only 5 minutes every hour.
- the dried hides had a clear blue tone, were well stretched without wrinkles or curves, and were very easy to machine mechanically; with regard to appearance and workability, the hides tanned by the process of the invention are at least comparable to, if not even better than, the wet blue hides obtained by the conventional process with pickling.
- a sample of hide produced in this example was also subjected to a shrinkage temperature measurement (Tg): no shrinkage occurred up to the maximum temperature allowed by the instrument; the shrinkage temperature of the sample is therefore above 100 °C, confirming the excellent preservation properties over time of the tanned hide.
- Tg shrinkage temperature measurement
- This example refers to the preparation of a wet white tanning process (with tannins) according to the invention.
- Example 1 the amounts of added components are indicated as a percentage on the weight of the hide and all the steps of the process take place under stirring by continuous rotation of the drum except the unloading steps or the intermittent stirring steps.
- the hides were subjected to an initial 20-minute washing treatment with 100% water at 30 °C which was then unloaded from the drum.
- the deliming step was carried out in two successive steps.
- non-ionic degreaser consisting of 2-propylethyl alcohol ethoxylate (content in the mixture 58%), 3% sodium salts of sulphates of C12-C14 alcohol ethoxylates and 0.04% 1 ,2-benzylisothiazol-3(2/-/)-one, the balance to 100% consisting of ammonium sulphate.
- the second step of the deliming step was carried out with 100% water at 36 °C by successive additions of components in the same solution.
- Maceration was then carried out by adding 0.2% of a mixture of 30% dicarboxylic acids and 1 % of a commercial pancreatic enzyme to the same solution deriving from deliming and the treatment was continued for 90 minutes, finally unloading the solution from the drum.
- the step of the preparation for tanning, characteristic of the invention was then carried out.
- 0.5% of a mixture of powdered C4-C6 dicarboxylic acids was added, continuing the treatment for 20 minutes, followed by 2% of sodium formate, continuing the treatment for a further 20 minutes.
- the tanning treatment was then carried out.
- the dried hides were cream to white in colour, were well stretched without wrinkles or creases, and were easy to machine mechanically; in these respects the hides tanned by the process of the invention are at least comparable to, if not even better than, the wet white hides obtained by the processes of the prior art.
- the shrinkage temperature of a sample of hide thus obtained was measured and found to be equal to 78 °C, confirming the excellent preservation properties over time.
- Some samples obtained from the thus tanned hides were also subjected to volatile organic compound (VOC) emission measurements.
- VOC volatile organic compound
- a hide from this example was pressed, split and shaved up to a thickness of 1.1 -1.2 mm, and a sample was taken from it and subjected to measurement using the method VDA 278:2011, and emissions of organic compounds equal to VOC 249 mg/Kg (expressed as toluene) and FOG 1373 mg/Kg (expressed as C16 hydrocarbons) were found.
- the second hide of the example was treated in the same way as the first hide, and three samples were taken from it and measured using the method VDA 277:1995-01, finding in the three measurements release values of volatile organic compounds equal to 22.8 pgC/g, 21.8 pgC/g and 20.9 pgC/g, respectively (the measurement unit pgC/g indicates the pg of carbon in the VOCs emitted per g of sample).
- the process of the invention makes it possible, in an unexpected way, to achieve this result without the need for a pickling step, with the consequent elimination from the process wastewater of acids such as sulphuric, formic and in some cases also hydrochloric acid, and the reduction in this water of 6-8% (by weight of the hides) of sodium chloride.
- the use of the special sulphonated oils in the characteristic process step, alternative to pickling, also enables a significant reduction in VOC and FOG (volatile organic compound emissions) values to be obtained in the final product.
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PCT/IB2021/056546 WO2022018632A1 (en) | 2020-07-22 | 2021-07-20 | Environmentally friendly process for tanning hides |
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